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Boron-Carbide and Boron Rich Rhobohedral Based Transistors and Tunnel Diodes

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Boron-Carbide and Boron Rich Rhobohedral Based Transistors and Tunnel Diodes University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln Peter Dowben Publications Research Papers in Physics and Astronomy July 2003 Boron-Carbide and Boron Rich Rhobohedral Based Transistors and Tunnel Diodes Peter A. Dowben University of Nebraska-Lincoln, [email protected] Follow this and additional works at: https://digitalcommons.unl.edu/physicsdowben Part of the Physics Commons Dowben, Peter A., "Boron-Carbide and Boron Rich Rhobohedral Based Transistors and Tunnel Diodes" (2003). Peter Dowben Publications. 74. https://digitalcommons.unl.edu/physicsdowben/74 This Article is brought to you for free and open access by the Research Papers in Physics and Astronomy at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Peter Dowben Publications by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. (12) United States Patent (10) Patent NO.: US 6,600,177 B2 Dowben (45) Date of Patent: Jul. 29,2003 (54) BORON-CARBIDE AND BORON RICH (56) References Cited RHOMBOHEDRAL BASED TRANSISTORS U.S. PATENT DOCUMENTS AND TUNNEL DIODES 6,025,611 A * 212000 Dowben ..................... 2571183 (75) Inventor: Peter A. Dowben, Crete, NE (US) * cited by examiner (73) Assignee: Board of Regents, University of Primary Examiner4eorge Fourson Nebraska-Lincoln, Lincoln, NE (US) Assistant Examiner-Thanh V Pham (74) Attorney, Agent, or FirmSuiter West PC LLO ( * ) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 (57) ABSTRACT U.S.C. 154(b) by 0 days. The present invention relates to the fabrication of a boron carbideboron semiconductor devices. The results suggest (21) Appl. No.: 091991,768 that with respect to the approximately 2 eV band gap pure boron material, 0.9 eV band gap boron carbide (B5C) acts as (22) Filed: Nov. 16, 2001 a p-type material. Both boron and boron carbide (B5C) thin (65) Prior Publication Data films were fabricated from single source borane cage mol- ecules using plasma enhanced chemical vapor deposition US 200210045300 A1 Apr. 18, 2002 (PECVD). Epitaxial growth does not appear to be a require- Related U.S. Application Data ment. We have doped boron carbide grown by plasma enhanced chemical vapor deposition. The source gas closo- 1,2-dicarbadecaboran' (orthbcarborane) was used to grow (60) Division of application No, 091465,044, filed on Dee 16, 1999, now Pat. No. 6,440,786, which is a continuation-in- the boron carbide while nickelocene (Ni(CsH5)2) was used vart of avvlication No. 091933,362, filed on Sev. 19, 1997, to introduce nickel into the nrowinn film. The dovinn of , , . , u u . u now P~~:NO.6,025,611. nickel transformed a B5C material p-type relative to lightly (60) Provisional application No. 601026,972, filed on S~P.20, doped n-type silicon to an n-type material, Both p-n hetero- 1996. iunction diodes and n-p heteroiunction diodes with n- and p-type Si [1,1,1] respectively. With sufficient partial pres- (51) Int. CL7 ........................................ HOlL 2110328 sures of nickelocene in the plasma reactor diodes with characteristic tunnel diode behavior can be successfully (52) U.S. C1. ........................ 2571183; 2571200; 2571201 fabricated, (58) Field of Search .......................... 2571183, 20CL201 15 Claims, 8 Drawing Sheets "" "-@ VDS (-1 Source Drain U.S. Patent Jul. 29,2003 Sheet 1 of 8 Applied Bias (V) FIG. la Applied Bias (v:) FIG. lb U.S. Patent Jul. 29,2003 Sheet 2 of 8 US 6,600,177 B2 Source Drain FIG. 2a 0.5 - -0 - -3.5 - tlrlrlflll~~,~~~~~l~~t - -5.5 -5.0 - 4.0 -3.0 - 2.0 -1 -0 0.0 0.5 VDS Drain Voltage (V) FIG. 2b U.S. Patent Jul. 29,2003 Sheet 3 of 8 U.S. Patent Jul. 29,2003 Sheet 4 of 8 U.S. Patent Jul. 29,2003 Sheet 5 of 8 U.S. Patent Jul. 29,2003 Sheet 6 of 8 U.S. Patent Jul. 29,2003 Sheet 7 of 8 Applied Bias (V) FIG. 5a Applied Bias (v) FIG. 56 U.S. Patent Jul. 29,2003 Sheet 8 of 8 FIG. 6 US 6,600,177 B2 1 2 BORON-CARBIDE AND BORON RICH Recent successes in construction of boron carbideln-Si RHOMBOHEDRAL BASED TRANSISTORS [1,1,1] heterojunction diodes [5,6] have demonstrated that AND TUNNEL DIODES boron carbidelsi [1,1,1] heterojunction diodes can be fab- ricated from closo-1,2-dicarbadodecaborane(C2BloH12; RELATED APPLICATIONS s orthocarborane) by using synchrotron radiation induced This application is a divisional of U.S. patent application chemical vapor deposition (SR-CVD) [5, 61, and plasma Ser. No. 091465,044, filed Dec. 16, 1999, now U.S. Pat. No. enhanced (PECVD) L2, 3, 5-71. 6,440,786, which is a continuation in part of U,S, patent Pure boron films also had been deposited on silicon from application Ser. No. 091933,362, now U.S. Pat. No. 6,025, nidO-decabOrane (B~oH~,;decabOrane) using SR-CVD 611 filed Sep. 19, 1997, which claims priority under 35 10 [8, 91. Boron carbidein-Si [1,1,1] heterojunction devices U.S.C. §119(e) to provisional application Ser. No. 601026, fabricated carbide nidO- 972, filed Sep. 20, 1996. Each of said applications is pentaborane and using PECVD is and incorporated herein by reference in its entirety. described in U.S. Pat. No. 5,468,978, hereby incorporated by reference in its entirety. GOVERNMENT RIGHTS IS SUMMARY OF THE INVENTION This work resulted in part from research conducted under U.S. Air Force grant AF~SRF49620-94-1-0433. The gov- It is an object of the present invention to provide boron1 ernment has certain rights in this invention. boron carbide and doped boron carbide semiconductor devices and techniquesto fabricate same. BACKGROUND OF THE INVENTION 20 It is another obiect of the vresent invention to vrovide a The present invention relates to a process for the depo- semiconductor device suited for use in high temperature, sition of boron carbide semiconductor material, and also to corrosive, mechanically abrasive, or radioactive environ- semiconductor devices formed by deposition of a boron ments. carbide film. The invention is more particularly directed to 25 ~~~~h~~ object of the present invention is to provide a technique for creating a layer of boron carbide with a boron carbide semiconductor devices and fabrication tech- boron-to-carbon ratio of about 5. The invention is also niques which do not require a silicon interface, particularly directed to semiconductor devices produced by Yet another object of the present invention is to provide this technique. boron carbide semiconductor devices and fabrication tech- Boron and boron carbide devices have been sought since 30 niques to fabricate same which do not depend on epitaxial 1959 [I] but only recently has the fabrication of these growth or crystallite size, devices been realized [2, 31. Such devices would have Still another object of the present invention is to provide applicability in a wide number of harsh conditions. For example, they should be resistant to corrosive, high doped boron carbide semiconductor devices and fabrication techniques for making same. In one embodiment, the doped temperature, and mechanically abrasive environments. 35 boron carbide appears as n-type relative to an n-type silicon Because of the large neutron capture cross-section, these substrate. materials could be used in devices in radioactive environ- ments as well [4]. The objects of the present invention are provided by the Techniques are known for forming boron-rich carbides, boronlboron carbide heterojunction devices and the doped These techniques may employ alkanes and heavy boron cage 40 boron carbidelsilicon semiconductor devices and fabrication molecules to deposit boron carbide thin films. Plasma- as herein. enhanced chemical vapor deposition (PECVD) can be The fabrication of several working boronlboron carbide employed to fabricate boron carbide films without resort to semiconductor devices is described herein. In an effort to high temperatures or high pressures, ~h~~~ technique typi- fabricate a more sophisticated device, a transistor was made cally employ a halide of boron, e.g., BCl,, BBr, or Bl,. Most 45 in a PECVD system. A diode was made directly on an recently boranes, such as nido-decaborane and nido- aluminum substrate to demonstrate that a silicon interface is pentaborane have gained interest, because these compoun~s not essential for fabrication of a boron carbide device. The are safe and stable, yet produce a vapor pressure of several Use of plasma enhanced chemical vapor deposition Torr at room temperature. However, until very recently, only (PECVD) provides a means for fabricating boron and boron low-resistivity boron carbide materials could be produced, so carbide thin films successfully in a high resistivity form [2, i.e., materials with resistivities on the order of about ten 31 The Present invention addresses some of the issues ohm-cm at room temperature, Boron carbide material of this associated with making devices of increasing complexity type has an extremely low band gap, and is not suited as a from boron carbide. semiconductor material. The aluminum substrates were polycrystalline, and the At the same time, boron carbide has become an attractive ss silicon substrates were [1,1,1], n-type. Both were chemically material because of its inherent hardness and durability, etched and cleaned prior to insertion in vacuo and set on the Boron carbide, like other boron-containing materials, has lower electrode. The substrates were further cleaned by Ar' been considered for high temperature electronic devices b~mbardmentat 300 mTOrrr, 40 W and annealed at 400' C. because it retains its useful characteristics at elevated tem- in the vacuum system. Deposition was carried out in a peratures. For example, boron carbide is known to have a 60 custom designed parallel plate 13.56 MHz radio-frequency melting temperature of 2350" C., a strength of 50 ksi, a plasma enhanced chemical vapor deposition (PECVD) reac- hardness of 2800 kgimm2, and a thermal conductivity of tor described previously [3,7].
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